Characterizing of directional solidification mode of Fe–Cr–Ni alloys during welding was performed using intense synchrotron radiation probe. Consequently, the crystal growth in the rapid solidification process was revealed in detail and the peak profile was systematically analyzed in order to acquire the essential information for controlling the weld microstructure. Then, the crystallization timing of the primary and secondary phases was discussed. Furthermore, the possibility of the lattice rotation to commensurate (i) each dendrite and (ii) crystallites in the dendrites is suggested.